Process for glycidyl 2 2-dinitro-2-fluoroethoxide

ABSTRACT

EPIBROMOHYDRIN IS REACTED WITH 2,2-DINITRO-2-FLUOROETHANOL IN A ONE STEP PROCESS TO PRODUCE GYCIDYL 2-DINITRO-2-FLUOROETHOIDE (GNDFE). THE CONDITIONS OF THE REACTION PREVENT THE FORMATION OF 1,3-BIS-(2,2-DINTRO-2FLUOROETHOA)-2-PROPANOL, A BY-PRODUCT ORDINARILY FORMED IN GDNFE PREPARATIONS, WHICH IS DIFFICULT TO SEPARATE FROM GDNFE. GDNFE IS USEFUL AS A BINDER FOR EXPLOSIVE AND PROPELLANT FORMULATIONS.

United States Patent 3,636,060 PROCESS FOR GLYCIDYL 2,2-DlNlTRO- 2-FLUOROETHOXIDE Milton B. Frankel, Tarzana, Edward F. Witucki, Sepulveda, and Ronald Rushworth, Reseda, Caliizl, assignors to the United States of America as represented by the Secretary of the Air Force N0 Drawing. Filed Mar. 4, 1970, Ser. No. 19,147 Int. Cl. C07d 1/18 US. Cl. 260348.6 Claims ABSTRACT OF THE DISCLOSURE Epibromohydrin is reacted with 2,2-dinitro-2-fluoroethanol in a one step process to produce glycidyl 2-dinitro-2-fiuoroethoxide (GDNFE). The conditions of the reaction prevent the formation of 1,3-bis-(2,2-dinitro-2- fiuoroethoxy)-2-propanol, a by-product ordinarily formed in GDNFE preparations, which is difficult to separate from GDNFE. GDN-FE is useful as a binder for explosive and propellant formulations.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention is in the field of organic preparations. More particularly, this invention relates to the preparation of glycidyl 2,2-dinitro-Z-fluoroethoxide (GDNFE) without the simultaneous formation of a by-product which is difiicult to separate from GDNFE.

(2) Description of the prior art Glycidyl 2,2-dinitro-2-fluoroethoxide (GDNFE) is known to be useful as a binder for explosive and propellant formulations. It has been prepared by a complicated, multistep process and it may be prepared by reacting epichlorohydrin with 2,2-dinitro-2-fiuoroethanol (FDNE) However, the reaction of epichlorohydrin with FDNE produces, in addition to the desired product, an equal amount of 1,3-bis-(2,2-dinitro-Z-fluoroethoxy)-2-propanol (BDNFEP) which 'is an undesirable by-product because it is difiicult to separate from GDNFE. The reaction pro duces a mixture of GDNFE and BDNFEP according to the following equations:

Separation of GDNFE from the mixture is difiicult because the chemical properties and boiling points of GDN'FE and BDNFEP are very similar. Complicated separation procedures have shown that the above reaction gives about a 33% yield of GDNFE in 45 hours.

Because of the complicated separation procedures necessary to separate the by-product, BDNFEP, when epi- Patented Jan. 18, 1972 Ice chlorohydrin is reacted with 2,2-dinitro-2-fluoroethanol and because of the complexity of the multistep process, a sample, reasonably fast, inexpensive method for preparing GDNFE has been a subject of interest, particularly in view of the potentially great value of GDNFE as a component of explosive and propellant formulations.

SUMMARY OF THE INVENTION DESCRIPTION OF THE PREFERRED EMBODIMENT Example I A mixture of 107.8 g. (0.64 mole) of 91.5% pure 2,2- dinitro-2-fluoroethanol and 87.6 g. (0.64 mole) of epibromohydrin was placed in a one-liter three-necked flask fitted with a mechanical stirrer, thermometer, and dropping funnel. The mixture was cooled to 02 C. in an icebath and a solution of 25.6 g. (0.64 mole) of sodium hydroxide in 225 ml. of water was added dropwise while maintaining the temperature at 02 C. The reaction mixture was then stirred at 2 C. for hours. Analysis of the lower organic layer by gas liquid chromatography showed the presence of 45 weight percent epibromohydrin, 16 weight percent 2,2-dinitro-Z-fluoroethanol, and 37 weight percent glycidyl 2,2-dinitro-2-fluoroethoxide (GDNzFE). The organic layer was separated and pumped with a high vacuum pump (0.05 mm. Hg pressure) overnight at ambient temperature to remove the volatile epibromohydrin. The residual liquid was taken up in 200 ml. of methylene chloride, washed four times with ml. portions of 5% sodium hydroxide solution and two times with 125 ml. portions of water. The'methylene chloride solution was then dried over calcium sulfate, filtered, and concentrated under vacuum at ambient temperature to give 43.8 g. (31.3% conversion) of GDNFE. The product was a light yellow liquid n 1.4350, 03 1.46. Analysis by gas liquid chromatography showed a purity of 99.6%.

Elemental analysis.Calcd. for C H N O F (percent): C, 28.60; H, 3.36; N, 13.33. Found (percent): C, 28.78; H, 3.29; N, 13.46.

The infrared spectrum was consistent with the assigned structure.

Example II A series of comparison reactions were carried out utilizing epichlorohydrin, epibromohydrin, varying reaction times, and varying reaction temperatures. When epichlorohydrin was used, 1,3-bis-(2,2-dinitro 2 fiuoro ethoxy)-2-propanol was always produced as a by-product. When epibromohydrin was used, but the reaction temperature was raised from 02 C. to 25 C., an unidentified by-product other than 1,3-bis(2,2-dinitro-2-fluoroethoxy)-2-propanol was produced. The comparison reactions are summarized in the following table. The unidentified by-product is designated as X.

TABLE-PROCESS STUDY ON PREPARATION OF GDNFE FROM EPIHALOHYDRIN (EHH) AND 2,2-DINITROQ-FLUORO (FDNE) E1111 FDNE GDNFE Analysis of reaction mizture by gas liquid chromato- Reaetion graphy (area percent)* Temp., time Epihalohydrin (EHH) 0. (hrs.) EHH FDNE X GDNFE BDNFEP" Epichlorohydrin 0-2 19 39 4 0 26 30 0-2 45 30 3 0 33 33 Epibromohydrin 0-2 24 61 11 0 23 0 0-2 48 48 12 0 32 0 0-2 70 45 16 0 37 0 25 27 33 23 13 21 0 *Area percentl s approzimate equal to weight percent. *CH2CHCHZO CHzC (N OmF +H 0 CHzC (N OmF We claim: 4. The method according to claim 1 wherein the tem- 1. The method for the preparation of glycidyl 2,2-dini- 25 Perature is from t0 tro-2-fluoroethoxide which comprises mixing and reacting accordlng to Clalm 1 Whemln the at a temperature below C. as equimolar mixture of Perature from to epibromohydrin, 2,Z-dinitro-2-fiuoro-ethanol, and sodium References Cited hydroxide catalyst.

I ED P TEN 2. The method according to claim 1 wherein the mixing UN T STATES A TS and reacting is conducted over a period of about 24 to 2314039 3/1943 Exans et a1 260348-6 X 70 hours.

NORMA S. MILESTONE, P a E 3. The method according to claim 1 in which glycidyl mm W Xammer 2,2-dinitro-2-fluoroethoxide is separated from the result- US, Cl. X R ing reaction mixture. 14988 

